CN103594683B - A kind of coating modification method preparing high temp. lithium ion battery manganate cathode material for lithium - Google Patents

Abstract

The invention discloses a coating modification method of spinel lithium manganese oxide and its application as a high-temperature lithium-ion battery positive electrode material. Its characteristic is that the lithium titanate coating layer grows directly on the surface of the lithium manganate crystal, and has the same lattice orientation as the lithium manganate crystal. In the present invention, the titanium source is first added to the suspension of lithium manganate, and then transferred to a polytetrafluoroethylene reactor at 80-200°C for 1-24 hours to obtain the final precursor of lithium manganate, and finally mixed with the lithium source Then calcining at 500-800° C. for 0.5-12 hours to obtain lithium manganate positive electrode materials with different coating amounts and different coating thicknesses coated with lithium titanate epitaxy. The coated and modified lithium manganate cathode material of the present invention has excellent normal temperature and high temperature cycle performance and rate performance. The problem of poor cycle performance and rate performance when lithium manganate is used as the positive electrode material of lithium ion batteries is solved.

Description

A coating modification method for preparing high-temperature lithium-ion battery lithium manganese oxide cathode material

technical field

The present invention relates to a method for coating and modifying lithium ion battery cathode materials, in particular to a method for preparing a high temperature lithium titanate coated lithium manganese oxide cathode material and lithium manganate based on the modification method as a lithium ion battery application of cathode materials.

Background technique

Lithium-ion batteries are widely used in portable electronic products such as mobile phones, notebooks and cameras due to their advantages of high energy density, high power density, high working voltage, low environmental pollution, and small self-discharge. At the same time, lithium-ion batteries are also the most competitive power source in the field of electric vehicles. Compared with traditional positive electrode materials such as lithium cobalt oxide, spinel lithium manganese oxide has the advantages of abundant resources, low price, environmental friendliness, and good safety, and has become the most potential positive electrode material for power batteries.

However, the capacity fading of spinel lithium manganese oxide is serious and the high-current charge-discharge performance is poor, especially in high-temperature environments, these defects are more obvious. This limits the large-scale commercial application of lithium manganate materials. The study found that the main reason for the severe capacity fading and poor high-current charge-discharge performance of lithium manganate is that the Mn ²⁺ produced by the disproportionation reaction of Mn ³⁺ in the material dissolves in the electrolyte, resulting in the loss of electrochemically active substances and the loss of manganic acid. The high oxidation of Mn ⁴⁺ in lithium materials leads to the decomposition of electrolyte on the surface of electrode materials.

A large number of studies have found that the surface coating modification of lithium manganate materials can effectively prevent the direct contact between the electrolyte and lithium manganate, reduce the dissolution of manganese and the decomposition of the electrolyte, thereby improving the electrochemical performance of lithium manganate. At present, the coating modification of lithium manganate is mainly coating with metal or non-metal oxides. Among the coating methods used, there are molten salt method, sol-gel method, mechanical mixing method, precipitation method, spray drying method and the like. However, in these coating methods, the coating layer is uneven, the coating thickness is difficult to control, and the binding force between the coating material and lithium manganate is poor. In addition, these metal oxides are poor in electrical conductivity and lithium ion conductivity. These defects make the cycle and rate performance of the modified lithium manganese oxide material still poor.

Li ₄ Ti ₅ O ₁₂ is a "zero strain" material, that is, it does not undergo structural changes during charging and discharging, and has become the research focus of lithium-ion battery anode materials in recent years. Li ₄ Ti ₅ O ₁₂ has higher lithium ion conductivity than lithium manganese oxide. Meanwhile, Li ₄ Ti ₅ O ₁₂ and lithium manganese oxide have the same spinel structure. Chinese Patent Publication No. CN1694285 uses Li ₄ Ti ₅ O ₁₂ as a coating layer to modify lithium manganate by sol-gel method. However, the coating layer obtained by this method is uneven, the thickness of the coating layer is relatively large, and the binding force between the coating layer material and lithium manganate is poor, so the cycle performance and rate performance of the material are actually still poor.

Contents of the invention

The technical problem to be solved by the present invention is to provide a method of coating modified lithium manganate with hydrothermal or solvothermal assistance, that is, to form a lithium manganate material on the surface of the lithium manganate material under the high temperature and high pressure conditions of the hydrothermal or solvothermal method. An amorphous layer of titanium oxide with uniform layer distribution and controllable thickness. In addition, the precursor is mixed with lithium source and sintered to obtain controllable thickness, uniform distribution of coating layer and consistent lattice orientation with lithium manganese oxide material Li ₄ Ti ₅ O ₁₂ coated LiMn ₂ O ₄ cathode material.

The technical solution of the present invention is: a Li ₄ Ti ₅ O ₁₂ coating modification method for improving the cycle performance and rate performance of the LiMn ₂ O ₄ positive electrode material of the lithium ion battery at room temperature (25°C) and high temperature (60°C). The steps are: add the titanium source compound solution into the suspension of LiMn ₂ O ₄ positive electrode material, mix well, transfer to the hydrothermal reaction kettle, the filling volume is 50%-85% of the volume of the reaction kettle, at 80-200 ℃, react for 1-48h, and obtain the precursor of LiMn ₂ O ₄ cathode material coated with titanium oxide. The obtained precursor is fully mixed with a lithium source compound in a suitable solvent, then dried at 60-120° C., and ground to obtain a precursor powder. Finally, the precursor powder is transferred to a high-temperature furnace and treated at a temperature of 500-800°C for 0.5-24 hours to obtain a Li ₄ Ti ₅ O ₁₂ -coated modified LiMn ₂ O ₄ positive electrode material, and the two crystal lattices have the same orientation .

The above cladding layer has a thickness of 3-200nm.

The mass ratio of the above cladding layer is 0.5-10%.

The titanium source compound solution mentioned above is: butyl titanate, isopropanol titanate, titanocene dichloride, titanium tetrachloride, titanium oxysulfate dissolved in water, methanol, ethanol, ethylene glycol, glycerol , butanol, acetone in one or more solvents formed.

The suspension of the above-mentioned LiMn ₂ O ₄ positive electrode material is a LiMn ₂ O ₄ positive electrode of various shapes synthesized by solid state method, sol-gel method, molten salt method, hydrothermal method, solvothermal method, and infiltration method. The material, with a particle size of 0.01-10 μm, is formed by suspending in one or more solvents of water, methanol, ethanol, ethylene glycol, glycerol, butanol and acetone.

The lithium salt mentioned above is one or more of lithium hydroxide, lithium acetate, lithium nitrate, lithium chloride, and lithium carbonate.

The above-mentioned solvent for mixing the precursor and the lithium source compound is one or more of water, methanol, ethanol, ethylene glycol, and acetone.

The Li ₄ Ti ₅ O ₁₂ coating modification method for the cycle performance and rate performance of the high-temperature lithium ion battery LiMn ₂ O ₄ cathode material prepared by the present invention has the following characteristics:

First, the cladding material Li ₄ Ti ₅ O ₁₂ grows directly on the surface of LiMn ₂ O ₄ and has the same lattice orientation as the host LiMn ₂ O ₄ .

Second, a uniform, thickness-controllable amorphous layer of titanium oxide is formed on the surface of the lithium manganate material by using hydrothermal or solvothermal high-temperature and high-pressure conditions.

Third, the ionic radius of Li ⁺ in soluble lithium salts is small, and it is easy to diffuse during heat treatment.

The above obtained LiMn ₂ O ₄ cathode material modified by coating with Li ₄ Ti ₅ O ₁₂ has greatly improved cycle stability and rate performance at room temperature (25°C) and high temperature (60°C), indicating that the use of The Li ₄ Ti ₅ O ₁₂ coating layer obtained by hydrothermal or solvothermal method can effectively prevent the direct contact between the electrolyte and lithium manganate, reduce the dissolution of manganese and the decomposition of the electrolyte, and has a strong affinity with lithium manganate of binding force. The hydrothermal or solvothermal method solves the problems of uneven distribution of coating layers obtained by common coating methods, difficult control of coating thickness, and poor binding force between coating materials and lithium manganate. Using Li ₄ Ti ₅ O ₁₂ with a high Li ⁺ diffusion coefficient as the cladding layer material solves the problem of poor conductivity of lithium ions when ordinary metal oxides are used as the cladding layer. Thus, the electrochemical performance of the material is improved. The invention has low cost, simple process route and low energy consumption, and is suitable for industrial mass production.

Description of drawings

Fig. 1 is the X-ray diffraction diagram illustrating the LiMn ₂ O ₄ positive electrode material coated with Li ₄ Ti ₅ O ₁₂ prepared in Example 1

Fig. 2 is the HR-TEM image illustrating the LiMn ₂ O ₄ positive electrode material coated with Li ₄ Ti ₅ O ₁₂ prepared in Example 1

FIG. 3 is a graph illustrating the cycle stability and rate performance of the Li ₄ Ti ₅ O ₁₂ coated and modified LiMn ₂ O ₄ positive electrode material prepared in Example 1 at room temperature (25° C.) and high temperature (60° C.).

Detailed ways

For a better understanding of the present invention, the present invention will be further described below in conjunction with examples, but the protection scope of the present invention is not limited to the expression range of examples.

Implementation Case 1

Add the ethanol solution of tetrabutyl titanate to the ethanol suspension of LiMn ₂ O ₄ (the mass ratio of LiMn ₂ O ₄ and tetrabutyl titanate is 10:1), and continue stirring for 20 minutes. Then, transfer it to a hydrothermal reaction kettle, keep it warm for 5 hours at 150°C, and after cooling to room temperature, filter and wash the precipitate several times to obtain an amorphous titanium oxide-coated lithium manganate precursor; The body is fully mixed with a certain amount of lithium hydroxide in an ethanol solution, dried at 80°C, and after grinding, it is treated in a high-temperature furnace at 700°C in an air atmosphere for 12 hours to obtain Li ₄ Ti ₅ O ₁₂ coating modification LiMn ₂ O ₄ cathode material. Figure 1 is an X-ray diffraction pattern, which shows that the coating modified material does not affect the spinel structure of the host material LiMn ₂ O ₄ . Figure 2 is a photo of the LiMn ₂ O ₄ positive electrode material after Li ₄ Ti ₅ O ₁₂ coating modification, showing that the Li ₄ Ti ₅ O ₁₂ coating layer is directly grown on the LiMn ₂ O ₄ host material, and the two have the same lattice orientation. The LiMn ₂ O ₄ cathode material modified by this method greatly improves the cycle stability and rate performance at room temperature (25°C) and high temperature (60°C). (See Figure 3 for its cycle and rate performance).

Preparation of positive electrode sheet and test of coin cell. LiMn ₂ O ₄ coated with Li ₄ Ti ₅ O ₁₂ is used as the active material of the electrode, conductive carbon black is used as the conductive agent, and polyvinylidene fluoride (PVDF) is used as the binder in a certain proportion (usually the mass ratio is 80:10:10), after adding N-methylpyrrolidone (NMP) solvent, grind and mix to obtain slurry. The slurry is coated on the aluminum foil of the current collector, and then vacuum-dried at 120°C for 8-10 hours to remove the solvent and moisture, and compacted under a pressure of 8-12MPa to make the powders of the electrodes contact closely. Then punch it into a positive electrode disc with a diameter of 14mm, and then dry it in a vacuum drying oven for 8-10 hours and prepare for assembly. Cells were assembled in a dry glove box filled with argon. The test battery is a CR2025 button battery, the negative electrode is a metal lithium sheet, the diaphragm is a Celgard2400 membrane, and the electrolyte is an electrolyte of 1MLiPF ₆ EC:DMC=1:1 (volume ratio). The battery test is carried out in the LANDCT-2001A battery test system, the charge and discharge voltage range is 3.0-4.5V, and the test temperature is 25 and 60°C respectively.

Implementation Case 2

Add the ethylene glycol solution of tetrabutyl titanate into the LiMn ₂ O ₄ ethylene glycol suspension (the mass ratio of LiMn ₂ O ₄ and tetrabutyl titanate is 10:1), and continue stirring for 20 minutes. Then, transfer it to a hydrothermal reaction kettle, keep it warm for 15 hours at 120°C, and after cooling to room temperature, filter and wash the precipitate several times to obtain an amorphous titanium oxide-coated lithium manganate precursor; The body is fully mixed with a certain amount of lithium nitrate in methanol solution, dried at 80°C, ground, and treated in a high-temperature furnace at 750°C for 10 hours in an air atmosphere to obtain Li ₄ Ti ₅ O ₁₂ coated modified LiMn ₂ O ₄ cathode material.

Implementation Case 3

Add the ethanol solution of tetrabutyl titanate to the ethanol suspension of LiMn ₂ O ₄ (the mass ratio of LiMn ₂ O ₄ and tetrabutyl titanate is 15:1), and continue stirring for 20 minutes. Then, transfer it to a hydrothermal reaction kettle, keep it warm for 2 hours at 200°C, and after cooling to room temperature, filter and wash the precipitate several times to obtain an amorphous titanium oxide-coated lithium manganate precursor; The body is fully mixed with a certain amount of lithium acetate in ethylene glycol solution, dried at 120°C, ground, and treated in an air atmosphere at 800°C in a high-temperature furnace for 5 hours to obtain Li ₄ Ti ₅ O ₁₂ coated modified LiMn ₂ O ₄ cathode material.

Implementation Case 4

Add the ethanol solution of isopropanol titanate to the ethanol suspension of LiMn ₂ O ₄ (the mass ratio of LiMn ₂ O ₄ to isopropanol titanate is 25:1), and continue stirring for 20 minutes. Then, transfer it to a hydrothermal reaction kettle, keep it warm for 24 hours at 80°C, and after cooling to room temperature, filter and wash the precipitate several times to obtain an amorphous titanium oxide-coated lithium manganate precursor; The body is fully mixed with a certain amount of lithium hydroxide in an ethanol solution, dried at 80°C, and after grinding, it is treated in a high-temperature furnace at 600°C in an air atmosphere for 24 hours to obtain Li ₄ Ti ₅ O ₁₂ coating modification LiMn ₂ O ₄ cathode material.

Implementation Case 5

Add the glycerol solution of isopropanol titanate into the glycerol suspension of LiMn ₂ O ₄ (the mass ratio of LiMn ₂ O ₄ and isopropanol titanate is 30:1), and continue stirring for 20 minutes . Then, transfer it to a hydrothermal reaction kettle, keep it warm for 5 hours at 200°C, and after cooling to room temperature, filter and wash the precipitate several times to obtain an amorphous titanium oxide-coated lithium manganate precursor; The body is fully mixed with a certain amount of lithium chloride in acetone solution, dried at 60°C, ground, and treated in a high-temperature furnace at 700°C for 15 hours in an air atmosphere to obtain Li ₄ Ti ₅ O ₁₂ coating modification LiMn ₂ O ₄ cathode material.

Implementation Case 6

Add the butanol solution of isopropanol titanate to the butanol suspension of LiMn ₂ O ₄ (the mass ratio of LiMn ₂ O ₄ and isopropanol titanate is 10:1), and continue stirring for 20 minutes. Then, transfer it to a hydrothermal reaction kettle, keep it warm for 12 hours at 200°C, and after cooling to room temperature, filter and wash the precipitate several times to obtain an amorphous titanium oxide-coated lithium manganate precursor; The body is fully mixed with a certain amount of lithium nitrate in an ethanol solution, dried at 80°C, ground, and treated in a high-temperature furnace at 650°C for 20 hours in an air atmosphere to obtain Li ₄ Ti ₅ O ₁₂ coated modified LiMn ₂ O ₄ cathode material.

Implementation Case 7

The aqueous solution of titanyl sulfate was added to the aqueous suspension of LiMn ₂ O ₄ (the mass ratio of LiMn ₂ O ₄ and titanyl sulfate was 10:1), and the stirring was continued for 20 minutes. Then, transfer it to a hydrothermal reaction kettle, keep it warm for 10 hours at 150°C, and after cooling to room temperature, filter and wash the precipitate several times to obtain an amorphous titanium oxide-coated lithium manganate precursor; The body is fully mixed with a certain amount of lithium hydroxide in an ethanol solution, dried at 100°C, and after grinding, it is treated in a high-temperature furnace at 750°C in an air atmosphere for 10 hours to obtain Li ₄ Ti ₅ O ₁₂ coating modification LiMn ₂ O ₄ cathode material.

Implementation Case 8

Add the ethanol solution of titanyl sulfate to the ethanol suspension of LiMn ₂ O ₄ (the mass ratio of LiMn ₂ O ₄ and titanyl sulfate is 15:1), and continue stirring for 20 minutes. Then, transfer it to a hydrothermal reaction kettle, keep it warm for 20 hours at 120°C, and after cooling to room temperature, filter and wash the precipitate several times to obtain an amorphous titanium oxide-coated lithium manganate precursor; The body is fully mixed with a certain amount of lithium acetate in methanol solution, dried at 60°C, ground, and treated in a high-temperature furnace at 600°C for 22 hours in an air atmosphere to obtain Li ₄ Ti ₅ O ₁₂ coated modified LiMn ₂ O ₄ cathode material.

Implementation Case 9

Dissolve titanyl sulfate in a mixed solution of water and ethanol with a volume ratio of 1:1, and then add it to the suspension of LiMn ₂ O ₄ in water and ethanol (wherein the mass ratio of LiMn ₂ O ₄ and titanyl sulfate is 20 :1), continue stirring for 20 minutes. Then, transfer it to a hydrothermal reaction kettle, keep it warm for 15 hours at 160°C, and after cooling to room temperature, filter and wash the precipitate several times to obtain an amorphous titanium oxide-coated lithium manganate precursor; The body is fully mixed with a certain amount of lithium hydroxide in ethylene glycol solution, dried at 120°C, and after grinding, it is treated in a high-temperature furnace at 750°C in an air atmosphere for 10 hours to obtain Li ₄ Ti ₅ O ₁₂ coating Modified LiMn ₂ O ₄ cathode material.

Implementation Case 10

Add the aqueous solution of titanocene dichloride to the aqueous suspension of LiMn ₂ O ₄ (the mass ratio of LiMn ₂ O ₄ to titanocene dichloride is 5:1), and continue to stir for 20 minutes. Then, transfer it to a hydrothermal reaction kettle, keep it warm for 12 hours at 180°C, and after cooling to room temperature, filter and wash the precipitate several times to obtain an amorphous titanium oxide-coated lithium manganate precursor; The body is fully mixed with a certain amount of lithium hydroxide in an ethanol solution, dried at 70°C, and after grinding, it is treated in a high-temperature furnace at 700°C in an air atmosphere for 14 hours to obtain Li ₄ Ti ₅ O ₁₂ coating modification LiMn ₂ O ₄ cathode material.

Implementation Case 11

Add the ethylene glycol solution of titanocene dichloride to the suspension of titanocene LiMn ₂ O ₄ in ethylene glycol (the mass ratio of titanocene LiMn ₂ O ₄ to titanocene dichloride is 10:1), and continue to stir for 20 minutes. Then, transfer it to a hydrothermal reaction kettle, keep it warm for 10 hours at 200°C, and after cooling to room temperature, filter and wash the precipitate several times to obtain an amorphous titanium oxide-coated lithium manganate precursor; The body and a certain amount of lithium chloride are fully mixed in acetone solution, dried at 60°C, and after grinding, they are treated in a high-temperature furnace at 800°C for 2 hours in an air atmosphere to obtain Li ₄ Ti ₅ O ₁₂ coated modified LiMn ₂ O ₄ cathode material.

Implementation Case 12

Add the ethanol solution of titanocene dichloride into the ethanol suspension of LiMn ₂ O ₄ (the mass ratio of LiMn ₂ O ₄ to titanocene dichloride is 20:1), and continue to stir for 20 minutes. Then, transfer it to a hydrothermal reaction kettle, keep it warm for 10 hours at 150°C, and after cooling to room temperature, filter and wash the precipitate several times to obtain an amorphous titanium oxide-coated lithium manganate precursor; The body is fully mixed with a certain amount of lithium hydroxide in an ethanol solution, dried at 90°C, and after grinding, it is treated in a high-temperature furnace at 700°C in an air atmosphere for 8 hours to obtain Li ₄ Ti ₅ O ₁₂ coated modified LiMn ₂ O ₄ cathode material.

Implementation Case 13

Add the aqueous solution of titanium tetrachloride to the aqueous suspension of LiMn ₂ O ₄ (the mass ratio of LiMn ₂ O ₄ and titanium tetrachloride is 50:1), and continue to stir for 20 minutes. Then, transfer it to a hydrothermal reaction kettle, keep it warm for 15 hours at 160°C, and after cooling to room temperature, filter and wash the precipitate several times to obtain an amorphous titanium oxide-coated lithium manganate precursor; The body is fully mixed with a certain amount of lithium nitrate in ethylene glycol solution, dried at 120°C, and after grinding, it is treated in a high-temperature furnace at 800°C in an air atmosphere for 5 hours to obtain Li ₄ Ti ₅ O ₁₂ coated modified LiMn ₂ O ₄ cathode material.

Implementation Case 14

Add the ethanol solution of titanium tetrachloride into the ethanol suspension of LiMn ₂ O ₄ (the mass ratio of LiMn ₂ O ₄ and titanium tetrachloride is 20:1), and continue to stir for 20 minutes. Then, transfer it to a hydrothermal reaction kettle, keep it warm for 12 hours at 140°C, and after cooling to room temperature, filter and wash the precipitate several times to obtain an amorphous titanium oxide-coated lithium manganate precursor; The body is fully mixed with a certain amount of lithium chloride in an ethanol solution, dried at 80°C, and after grinding, it is treated in a high-temperature furnace at 750°C in an air atmosphere for 8 hours to obtain Li ₄ Ti ₅ O ₁₂ coated modified LiMn ₂ O ₄ cathode material.

Implementation Case 15

Add the ethylene glycol solution of titanium tetrachloride to the ethylene glycol suspension of LiMn ₂ O ₄ (the mass ratio of LiMn ₂ O ₄ and titanium tetrachloride is 10:1), and continue to stir for 20 minutes. Then, transfer it to a hydrothermal reaction kettle, keep it warm for 24 hours at 180°C, and after cooling to room temperature, filter and wash the precipitate several times to obtain an amorphous titanium oxide-coated lithium manganate precursor; The body is fully mixed with a certain amount of lithium hydroxide in an ethanol solution, dried at 80°C, and after grinding, it is treated in a high-temperature furnace at 750°C for 12 hours in an air atmosphere to obtain Li ₄ Ti ₅ O ₁₂ coating modification LiMn ₂ O ₄ cathode material.

Claims (9)

1. a high temperature LiMn ₂o ₄the coating modification method of positive electrode, comprises the steps:

(1) titanium source compound and LiMn is taken respectively according to a certain percentage ₂o ₄positive electrode, and by titanium source compound wiring solution-forming, by LiMn ₂o ₄positive electrode dispersion forms suspension in a solvent;

(2) titanium source compound solution is joined LiMn ₂o ₄in the suspension of positive electrode, be fully uniformly mixed;

(3) mixed suspension is transferred in polytetrafluoroethyllining lining, puts into stainless steel reactor, carry out hydro-thermal reaction or solvent thermal reaction;

(4) presoma of step (3) gained and Li source compound are fully mixed in suitable solvent, then dry under 60-120 DEG C of condition, obtain precursor powder after grinding;

(5) by the heat treatment in air atmosphere of step (4) gained precursor powder, Li is obtained ₄ti ₅o ₁₂coating modification LiMn ₂o ₄positive electrode.

2. coating modification method as claimed in claim 1, is characterized in that: described titanium source compound is butyl titanate, metatitanic acid isopropyl alcohol ester, cyclopentadienyl titanium dichloride, titanium tetrachloride, titanyl sulfate; Be one or more in water, methyl alcohol, ethanol, ethylene glycol, glycerol, butanols, acetone for dissolving the solvent of titanium source compound.

3. coating modification method as claimed in claim 1, is characterized in that: LiMn described in step (1) ₂o ₄positive electrode is the LiMn of the various patterns by solid state process, sol-gal process, molten salt growth method, hydro thermal method, solvent-thermal method, infusion method synthesis ₂o ₄positive electrode, particle size is 0.01-10 μm; LiMn ₂o ₄positive electrode be suspended in aqueous solvent, methyl alcohol, ethanol, ethylene glycol, glycerol, butanols, acetone one or more.

4. coating modification method as claimed in claim 1, is characterized in that: described Li source compound is one or more in lithium hydroxide, lithium acetate, lithium nitrate, lithium chloride, lithium carbonate.

5. coating modification method as claimed in claim 1, is characterized in that: the solvent of mixing presoma and Li source compound is one or more in water, methyl alcohol, ethanol, ethylene glycol, acetone.

6. coating modification method as claimed in claim 1, is characterized in that: described hydro-thermal reaction or solvent thermal reaction are at 80-200 DEG C, and reaction 1-48h, the charging quantity of reactor is the 50%-85% of reactor volume.

7. coating modification method as claimed in claim 1, is characterized in that: described heat treatment adopts one-step or two-step method at 500-800 DEG C of heat treatment 0.5-24 hour.

8. coating modification method as claimed in claim 1, is characterized in that: described Li ₄ti ₅o ₁₂the thickness of coating layer is at 3-200nm.

9. coating modification method as claimed in claim 1, is characterized in that: described Li ₄ti ₅o ₁₂after coating layer accounts for coating modification, the mass ratio of LiMn2O4 is 0.5-10%.